1938-13 Workshop on Nanoscience for Solar Energy Conversion 27 - 29 October 2008 Reduced and Doped TiO2: what is the nature of the defect states? Gianfranco PACCHIONI Universita degli Studi di Milano-Bicocca Dipt. Scienza dei Materiali Via R. Cozzi 53 20125 Milano Italy Workshop on “Nanoscience for solar energy conversion”, Trieste, October 27-29, 2008 Reduced and doped TiO2: what is the nature of the defect states? G. Pacchioni, E. Finazzi, C. Di Valentin Dipartimento di Scienza dei Materiali Università Milano-Bicocca, Milan (Italy) A. Selloni Department of Chemistry, Princeton University, Princeton (USA) A. Czoska, M. C. Paganini, M. Chiesa, S. Livraghi, E. Giamello Dipartimento di Chimica IFM, Università di Torino (Italy) TiO2 polymorphs Anatase, Eg = 3.2 eV Ti-Ti 3.79 Å 3.04 Å rutile, Eg = 3.0 eV Ti-Ti 3.57 Å 2.96 Å TiO2: very important role of defects Color change in TiO2 samples induced by incresing level of defects Defects change electronic properties of the material Defect engineering of TiO2 for photocatalytic applications Main defects: oxygen vacancies, Ti3+ ions OUTLINE Part I : intrinsic defects O vacancies and Ti interstitials Part II : extrinsic defects N impurities and their interplay with other defects What is the nature of “reduced titania”? Excess of metal compared to oxygen results in formation of “Ti3+” ions. But … TiO2-x Ti1+xO2 O vacancies Ti interstitials Experimental proofs of formation of reduced bulk titania: (1) UV-vis (2) UPS (3) XPS (4) EPR Every theoretical method dealing with reduced TiO2 should be able to reproduce these features… (1) absorption bands in the visible region responsible for the change in color (assigned to d-d transitions) (2) occurrence of a new state in the gap at about 0.8 eV below the conduction band attributed to the reduced Ti3+ ions (3) shift in the core level binding energies of the reduced Ti atoms from Xray photoemission (XPS) (4) presence of more than one EPR signal associated to various kinds of paramagnetic Ti3+ ions in the lattice Ti4+ Ti3+ DFT calculations QUANTUM EXPRESSO (pure DFT, DFT+U) plane-wave-pseudopotential approach PBE functional – spin polarized calculations 96-atoms supercells anatase CRYSTAL06 (hybrid DFT) atomic gaussian basis set approach Hybrid DFT functionals – spin polarized calculation hyperfine coupling constants (EPR) rutile O vacancy in bulk anatase: standard DFT Eg 2.6 eV No states in the gap, electrons fully delocalized, no major geometrical distortion around the defect Problem due to self-interaction in DFT Pragmatic ways to improve the model DFT+U methods Systems where atomic-like features are persistent in the solid: explicit description of correlation by an on-site correlation term U for a few selected localized orbitals Add a Hubbard-like EHub term to the standard functional: Anisimov et al., Phys. Rev. B 44, 943 (1991) Hybrid functionals Use of hybrid functionals where HF-like exchange is mixed in with the DFT exchange: B3LYP (20%), H&H LYP (50%) Becke J. Chem. Phys. 98, 5648 (1993) O vacancy in bulk anatase: B3LYP and DFT+U Remove an O atom: 2e left on the system. Quantities of interest: (1) Energy gap (Eg) (2) Distance of impurity levels from bottom of conduction band ('E1, 'E2) B3LYP 'E1 1.2 eV 'E2 1.3 eV Both electrons are localized on Ti 3d levels ... DFT+U Ti3+ Eg 3.9 eV (U = 3 eV) Eg 2.8 eV 'E1 0.6 eV 'E2 0.9 eV ...but delocalized solution is close in energy Finazzi, Di Valentin, Selloni, GP, J. Chem. Phys. 128, 182505 (2008) Similar results for rutile (110) surface B3LYP xc functional, c(4x2) surface cell, AO Gaussian basis sets, spin polarized calculations, CRYSTAL03 O vacancy: two electrons localized on two nonequivalent Ti ions triplet ground state (magnetic) Two states in the gap at 1.2 and 0.9 eV below conduction band (as in the experiment) Di Valentin, GP, Selloni, Phys. Rev. Lett. 97, 166803 (2006) Polaronic nature of O vacancy O vacancy in rutile TiO2(110): strong distortion around the defect (similar for hydroxilated surface, where Ti3+ forms) Geometry: B3LYP DOS: B3LYP localization Geometry: B3LYP DOS: PBE localization Geometry: PBE DOS: B3LYP no localization Distortion essential to induce localization but present only using hybrid DFT methods Geometry: PBE DOS: PBE no localization Di Valentin et al. Chem. Phys. 339, 44 (2007) Reduced titania: a problem for theory Pure functionals fail to reproduce the correct band structure DFT+U or hybrid functionals improve the description but suffer from the use of “empirical” parameters Need to compare different approaches Need for clean experimental data (often missing) Generate defects in controlled way and characterize them by various spectroscopies (central role of EPR) In summary ... F and Nb doping of stoichiometric TiO2 leads to lattice Ti3+ ions in pseudo-octahedral enviornment H doping of stoichiometric TiO2 leads to the same lattice Ti3+ ions Reduction of stoichiometric TiO2 in mild conditions leads mainly to lattice Ti3+ ions Strong evidence from comparison of measured and computed EPR spectra of localized Ti 3d states at low T Only hybrid or DFT+U functionals lead to electron localization Localized and delocalized states are very close in energy and can depend on external conditions (T, P, etc.) New experiments: delocalization is a temperature effect? Delocalization of trapped electron occurs at RT (but here good agreement for the wrong reason: DFT calculations done at 0 K!) Barrier for e migration from site to site <0.1 eV (see M. Dupuis lecutre). At RT e is mobile on the time scale of experiment Reduced titania: oxygen vacancies versus Ti interstitials increasing annealing temperature o surface TiO2 TiO2x TiO Ti subsurface TiO2 TiO2x TiO2x TiO bulk TiO2 TiO2 TiO2x Ti1+xO2 Stoichiometric sample, colorless O diffusion from bulk to surface O vacancies form in subsurface regions Lattice Ti3+ (localized states at low T) Ti diffusion from surface to bulk Ti interstitials form in subsurface regions Titania in photoelectrolysis and photocatalysis APPLICATIONS (3) Final products: CO2 and Water (1) Organic pollutant adsorbes to surface (2) Adsorbed pollutant breaks down photocatalyst - Photoelectrolysis of H2O with TiO2 electrode (1970s) - Photocatalytic production of H2 (1980s) - Photocatalytic oxidation of organic molecules (1990s) - Photoinduced hydrophilicity - Self-cleaning, air and water purification, self-sterilizing - Band-gap photoexcitation - Electron-hole recombination - Migration to surface - Charge carrier trapping - Charge transfer J.T. Yates Jr. et al. , Chem. Rev. 1995 Photocatalysis by pure TiO2 B-x e- E cb B B-x e- E cb B hQ (UV) A A+x Photocatalysis by doped TiO2 h+ Pure TiO2: band gap does not allow to capture most part of solar light (only a small portion of the solar spectrum is absorbed) vb A A+x hQ (VIS) h+ vb Reduction of band gap obtained by inclusion of dopants: transition metals (V, Cr, Mn, Fe) or main group atoms (N, C, S, F) Properties of sol-gel prepared anatase N-doped TiO2 EPR TiO2 Sim. Sper. N-TiO2 3300 3320 3340 3360 3380 3400 B/Gauss TiO2 %R N-doped Anatase Anatase U.V. N-TiO2 CB Two paramagnetic species detected (EPR) - Weakly physisorbed molecular NO - Stable bulk species (responsible for yellow color) a.u. Abs Vis. VB 400 300 400 500 nm 600 700 800 UV-vis absorption spectra of pure and N-doped anatase 500 0 600 nm 1 700 800 2 3 Time (h) 4 5 Rate of methylene-blue degradation on N-doped (a) and pure (b) anatase DOPED TiO2: WHERE ARE THE DOPANTS? interstitial (bound to lattice O) or substitutional (to O or Ti atoms) Distinction possible by XPS? Simple (but often misleading) interpretation: Peak at 400-401 eV: interstitial N (N-O, N-H, etc.) Peak at 396-397 eV: substitutional N (Ti-N) XPS not always conclusive NITROGEN DOPED ANATASE: DFT (PBE) substitutional Nitrogen Nsub O N O Ti O O Ti interstitial Nitrogen Nint O Ti O O Ti O O O Ti Ti O O N Ti N 2p 0.14 eV vb O Ti Ti O O O Ti Ti O 2.6 eV 2.6 eV Ti O N cb cb Ti O O Ti Ti S* N-O N Ti 0.73 eV vb Both interstitial and substitutional N (paramagnetic) introduce localized states above the O 2p valence band Substitutional versus interstital N-doping: EPR Ti Ti N Ti Nsub EPR A1(N), G A2(N), G A3(N), G exp 2.4 4.2 32.5 Nint 0.2 1.8 33.4 Nsub 2.5 2.8 38.2 O Ti Ti N Ti Nint EPR: confirms localized nature of N-induced states in the gap Theory: PBE (Espresso) and B3LYP (Crystal03) calculations show similar level of localization. EPR properties computed at B3LYP level Hyperfine coupling constants: interstitial Nint more likely than substitutional Nsub (consistent with XPS) Di Valentin, Pacchioni, Selloni, Livraghi, Giamello, J. Phys. Chem. B 109 (2005) 11414 Messagge from EPR and theory: Stable N-species exist in the bulk Most likely interestitial N is formed N-induced states are localized! A conclusion of purely theoretical interest? Interplay between N-doping and oxygen vacancies DFT predicts: N-doping favors vacancy formation Energy cost to form Vo pure TiO2: 4.2 eV N-doped TiO2: 0.6 eV Ns-doping stabilized by the presence of oxygen vacancies (NS-O+VO) most stable situation under oxygen-poor conditions Di Valentin, Pacchioni, Selloni, Livraghi, Giamello, J. Phys. Chem. B 109, 11414 (2005) Di Valentin, Pacchioni, Selloni, Chem. Materials 17, 6656 (2005) Interplay between Ti3+ states and N-impurities cb Nbx 3d1 Ti3+ 3d0 Ti4+ Nb vb DFT predicts: spontaneous charge transfer from Ti3+(3d)1 to Nb formation of Ti4+ and Nb centers (singlet state, lower by 3 eV than triplet state) Nb centers introduce states above O 2p valence band as neutral Nb states Di Valentin, Pacchioni, Selloni, Livraghi, Giamello, J. Phys. Chem. B 109 (2005) 11414 Experimental proof: reaction of TiO2 with atomic N Nx Reduced TiO2 powders exposed to atomic N: decrease of Ti3+(3d)1 signal until it is completely quenched Chiesa, Giamello (2008) g3 = 2.003 Ti3+ Batzill, Morales, Diebold, Phys. Rev. Lett. 96, 026103 (2006) Increasing N exposure TiO2 single crystal: N implantation reduces peak due to Ti3+(3d)1 states in UPS 3000 A3 = 3.23 mT 333 334 335 336 337 338 339 340 B / mT 341 342 a b c d Nx 3100 3200 3300 3400 e 3500 B / Gauss 3600 3700 3800 3900 An interesting experiment on N-doped samples N b Blue + O2 Lamp Lamp off off Blue Blue 3.5 I/I 0 3.0 (a.u.) 2.5 EPR of N-doped TiO2 under irradiation Reversible creation of Nbx paramagnetic centers (b = bulk) Lamp off 2.0 1.5 Green O2x 1.0 0.5 0.0 0 50 100 Time (min) 150 Light induces conversion of diamagnetic precursors into paramagnetic centers Irradiation under O2: O2 captures one electron from TiO2 surface and forms O2O2 acts as electron scavanger Livraghi, Paganini, Giamello, Selloni, Di Valentin, Pacchioni J. Am. Chem. Soc. 128, 15666 (2006) Generation of paramagnetic defects under irradiation N-doped TiO2 e CB vis-hQ Nb Nb VB Process completely reversible by turning light off Adsorbed O2 as electron scavanger N-doped TiO2 O2 e CB vis-hQ Nb O2 x Nbx VB Process irreversible under O2 exposure; formation of O2 N-states responsible for photo-activity of N-doped TiO2 EPR and DFT show unambiguously the localized nature of N-induces states in TiO2 N dopants favor formation of oxygen vacancies in the material (Ti3+ states); vacacies can become hydroxilated (same behaviour) Charge transfer occurs from Ti3+ states (high in the gap) and singly occupied N-states (low in the gap): Ti3+ + Nbx o Ti4+ + Nb Visible light induces conversion of diamagnetic precursors into paramagnetic centers by excitation of electrons to the conduction band (Nb + hQ o Nbx) Excited electrons are captured by O2 adsorbed on the surface (formation of paramagnetic O2) N-states responsible for photo-activity of N-doped TiO2 Livia Giordano Lorenzo Ferraro Cristiana Di Valentin Annabella Selloni Matteo Frigerio Fabrizio Cinquini Sabrina Sicolo Umberto Martinez Elio Giamello Emanuele Finazzi
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